Cyan image-providing phenylazonaphthyl dyes

ABSTRACT

WHEREIN Car represents a p-sulfonamidophenol or p-sulfonamidonapthol carrier moiety which, as a function of oxidation under alkaline conditions, releases a diffusible dye; X represents a bivalent linking group; R represents hydrogen or alkyl; J represents sulfonyl or carbonyl; M AND Q EACH REPRESENT AN INTEGER HAVING A VALUE OF 0 OR 1; Q represents hydrogen, hydroxy or an acylamino; G represents hydroxy, a salt thereof, or a hydrolyzable acyloxy group; D represents halogen, cyano, nitro, trifluoromethyl, alkyl, alkoxy, carboxy, a carboxylic acid ester, fluorosulfonyl, a SO3-phenyl radical, sulfo, a sulfamoyl radical, an alkylsulfonyl radical, a phenylsulfonyl radical or D can represent a substituent having the formula CAR-(X-(NR-Jq)m- or CAR-X-J-, provided that the CAR-(X-(NR-J)q)m- substituent on the naphthalene nucleus of Formula I is replaced by an M group or the CAR-X-J-NH- substituent on the naphthalene nucleus of Formula II is replaced by a Q group wherein Car, X, J, R, q and m are as described previously; E represents hydrogen, halogen, nitro, cyano or trifluromethyl; M represents hydrogen, carboxy, a carboxylic acid ester, sulfo, a sulfamoyl radical, a carbamoyl radical, an alkylsulfonyl radical, or a phenylsulfonyl radical; WITH THE PROVISO THAT THERE BE NO MORE THAN ONE SULFO RADICAL AND NO MORE THAN ONE CARBOXY RADICAL PRESENT IN SAID COMPOUND.   Cyan azo dye-providing compounds having the formula

United States Patent n 1 3,929,760

Landholm et al. Dec. 30, 1975 [54] CYAN IMAGE-PROVIDING QPHENYLAZONAPHTHYL DYES e+o [75] Inventors: Richard A. Landholm; Jan R.-[X-(NRJ) D\' Haase, both of Rochester, N.Y.; \FNOZ lrames J. Krutak,Sr., Kingsport, E

enn.

(73] Assignee: Eastman Kodak Company,

Rochester, NY H or: [22] Filed: Feb. 5, 1974 ,/.j j\

21 Appl. No.: 439,788 Car-XJNR-\- R Related US. Application Data Gag2oN:N-o E [63] Continuation-impart of Ser. No. 143L727, Feb. 12,

i973, abandoned.

wherein [1.8. CI. Cal represents a u]fonamido heno| or 260/202; 260/456A; 260/543 R; 260/556 A; 2601556 B; 260/556 C; 260/559 S [51] Int.Cl.C09B 29/10; C09B 29/20; 003C 5/30;

[58] Field of Search 260/197, I98, 199, 200, 260/202, 20]; 96/3p-sulfonamidonapthol carrier moiety which, as a function of oxidationunder alkaline conditions, releases a diffusible dye;

X represents a bivalent linking group;

R represents hydrogen or alkyl;

.l represents sulfonyl or carbonyl;

m and q each represent an integer having a value of Q representshydrogen, hydroxy or an acylamino;

G represents hydroxy, a salt thereof, or a hydrolyzable acyloxy group;

[56} Referances cued D represents halogen, cyano, nitro,trifluoromethyl,

UNITED STATES PATENTS alkyl, alkoky, carboxy, a carboxylic acid ester,2,706,684 4/l955 Graham et 260/202X fluorosulfonyl, a ---SO;,-phenylradical, sulfo, a 3,l48,062 9/1964 Whitmore et al 96/55 sulfamoylradical, an alkylsulfonyl radical, a 3l443l939 5/1969 95/3phenylsulfonyl radical or D can represent a 3,443,940 5/1969 Bloom etal. 96/3 substiwem having the formula 3,459,548 8/1969 Bloom etal. 96/3or 3,498,785 3/l970 Bloom etalm 96/3 d h h CAR x NR J 3,585,028 6/l97lStephens 96/3 M 3,628 952 l2/I97l Puscheletal 96/3 Sub-Went naphthalenenudeus of 3,709,693 l/l973 Bloom etal. 96/118 Formula I Is replaced y Mgroup or the 3,737,316 6/1973 Salminen etal... .96/56.6 H substltuent onthe 3,751,406 8/I973 260 162 naphthalene nucleus of Formula ll isreplaced by a Q group wherein Car, X, J, R, q and m are as describedpreviously;

E represents hydrogen, halogen, nitro, cyano or trlfluromethyl;

M represents hydrogen, carboxy, a carboxylic acid ester, sulfo, asulfamoyl radical, a carbamoyl Primary ExaminerFloyd D. Higel AssistantExaminer-Doll John J. Attorney, Agent, or Firm-Elliott Stern; Daniel B.

Reecel m radical, an alkylsulfonyl radical, or a phenylsulfonyl radical;

with the proviso that there be no more than one [57] ABSTRACT sulforadical and no more than one carboxy radical present in said compound.Cyan azo dye-provldlng compounds havmg the formula 14 Claims, NoDrawings CYAN IMAGE-PROVIDING PHENYLAZONAPHTHYL DYES This is acontinuation-impart application of U.S. Ser. No. 33l,727, filed Feb. l2,I973, now abandoned.

This invention relates to the art of photography and more particularly,to color diffusion transfer photography employing cyan dye-providingcompounds.

Color diffusion transfer processes generally involve the use of aphotographic element comprising a support, at least one silver halideemulsion layer and an image dye-providing material which is contained inor contiguous said layer. The im'age dye-providing material typicallycan be thought of as having the structure Car-Col wherein Col is acolorant such as a dye or a dye precursor and Car is an associatedcarrier or monitoring group which as a function of alkaline processingeffects a substantial change in the diffusivity of at least the Colportion of the compound.

After exposure, a photographic element as described above is treatedwith an alkaline processing solution to effect imagewise discriminationin the element. As mentioned previously, the imagewise discrimination isgenerally brought about by the monitoring or carrier group which, in thepresence of the alkaline processing solution, is responsible for asubstantial change in the diffusivity of at least the dye portion of thedye-providing material. As is known in the art, the dye-providingmaterial can be initially immobile or initially mobile in the processingsolution. Upon alkaline processing of an initially immobiledye-providing material, a mobile dye can be released imagewise or thematerial can be imagewise rendered soluble and thus mobile. If thematerial is initially mobile, the processing solution typically rendersthe material insoluble (and thus immobile) in an imagewise fashion.

It is well known in the art to utilize image dye-providing materials ina photographic element wherein an imagewise exposed element can becontacted with an alkaline processing solution to effect an imagewisedifference in mobility of at least a portion of the dyeprovidingmaterial, i".e., to effect release of a dye or dye precursor, to rendersaid compound insoluble or soluble. It is the particular carrier ormonitoring group which determines what form the change in diffusivity(of at least the dye portion of the material) will take. In certaininstances, an increase in solubility of a given compound can beaccomplished by substantially reducing the molecular weight of thecompound; see, for example, the disclosure of Gompf US. Pat. No.3,698,897, issued Oct. I7, I972, in Fleckenstein et al. allowed Ser. No.351,763, a continuation-impart of Ser. No. 282,796, filed Aug. 22, I972,and now abandoned, entitled PHOTOGRAPHIC SYSTEMS and in Anderson et al.US. Pat. No. 3,725,062, filed July 6, I97 I entitled COLOR DIFFUSIONTRANSFER PROCESSES. Exemplary of systems wherein the dyeprovidingcompound splits off a dye are those described in Whitmore US. Pat. No.3,227,552, issued .Ian. 4, I966, and Bloom US. Pat. No. 3,443,940,issued May l3, I969, and Canadian Pat. No. 602,607, issued Aug. 2, I960.Similarly, Yutzy US. Pat. No. 2,756,142, issued July 24, 1956, US. Pat.No. 2,774,668, issued Dec. l8, I956, and US. Pat. No.

2 2,983,606, issued May 9, I961, describe photographic elements whereina dye-providing compound is rendered immobile in an imagewise fashion.

All of these prior systems have utility; however, it is desired toprovide new compounds which provide new dyes having especiallyadvantageous properties, such as improved hue, diffusibility,mordantability and the like.

We have found a class of cyan, azo dye-providing compounds well suitedfor use in color diffusion transfer color elements. The dye-providingcompounds, as a function of typical processing under alkalineconditions, provide a cyan-colored substance having a mobility differentthan that of the compound.

The objects of the present invention are achieved through the use, incolor diffusion transfer elements, of a new class of cyan, azodye-providing compounds as well as the dyes provided thereby. Typically,these compounds are utilized in a photosensitive element which comprisesa support having thereon at least one photosensitive silver halideemulsion, and at least one of said layers having associated therewith acyan, azo dye-providing compound of this invention.

The compounds of this invention can be represented by the followingformulas:

Car represents a carrier moiety which, as a function of oxidation underalkaline conditions, provides a substance having a mobility differentthan that of said compound;

X represents a bivalent linking group of the formula R'L,,R',, whereeach R can be the same or different and each represents an alkyleneradical having 1 to about 8 carbon atoms; a phenylene radical; or asubstituted phenylene radical having 6 to about 9 carbon atoms; Lrepresents a bivalent radical selected from oxy, carbonyl, carboxamido,carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl; n is an integerhaving a value ofO or l;p is I when n equals I and p is I or 0 when nequals 0, provided that when p is I the carbon content of the sum ofboth R radicals does not exceed 14 carbon atoms;

R represents a hydrogen atom, or an alkyl radical having I to about 6carbon atoms;

J represents a bivalent radical selected from sulfonyl or carbonyl;

m and q each represent an integer having a value of or I; Q represents ahydrogen atom, a hydroxy radical, or a radical having the formula NHCORor NHSO R wherein R is an alkyl radical having 1 to about 6 carbonatoms, a substituted alkyl radical having 1 to about 6 carbon atoms,benzyl, phenyl, or a substituted phenyl radical having 6 to about 9carbon atoms;

G represents a hydroxy radical, a salt thereof, or a hydrolyzableacyloxy group having the formula:

wherein R is an alkyl radical having l to about 18 carbon atoms, phenylor substituted phenyl having 6 to about 18 carbon atoms;

D represents a halogen atom, a cyano radical, a nitro radical, atrifluoromethyl radical, an alkyl radical having 1 to about 6 carbonatoms, an alkoxy radical having 1 to about 6 carbon atoms, a carboxyradical, a carboxylic acid ester having the formula COOR wherein R is asdescribed previously, a fluorosulfonyl radical, a SO -phenyl radical ora substituted SO phenyl radical having 6 to about 9 carbon atoms, asulfo radical, a sulfamoyl radical having the formula -SO NR R" whereinR represents hydrogen or an alkyl group having 1 to about 6 carbon atomsand R represents hydrogen, an alkyl radical having I to about 6 carbonatoms, a substituted alkyl radical having 1 to about 6 carbon atoms, abenzyl radical, a phenyl radical, a substituted phenyl radical having 6to about 9 carbon atoms, an alkyl carbonyl radical having 1 to about 8carbon atoms, or a phenyl carbonyl radical having 6 to about 9 carbonatoms, with the proviso that the carbon content of the sum of R and Rnot exceed 14 carbon atoms; a carbamoyl radical having the formula CON(Rwherein each R can be the same or different and is as describedpreviously; an alkylor substituted alkylsulfonyl radical having 1 toabout 8 carbon atoms, a phenylor substituted phenyl-sulfonyl radicalhaving 6 to about 9 carbon atoms; or D can represent a substituenthaving the formula CAR-[X- (NRJ),,],,, or CARX-J, provided that theCAR-[X(NRJ) substituent on the naphthalene nucleus of Formula I isreplaced by an M group or the CARX-JNH substituent on the naphthalenenucleus of Formula II is replaced by a 0 group wherein Car, X, J, R, qand m are as described previously.

E represents a hydrogen atom, a halogen atom, a nitro radical, a cyanoradical or a trifluoromethyl radical;

M represents a hydrogen atom, a carboxy radical, a carboxylic acid esterhaving the formula COOR wherein R is as described previously, a sulforadical, a sulfamoyl radical having the formula SO NR"'R a carbamoylradical having the formula CON(R) wherein R and R are as describedpreviously, an alkylor substituted alkylsulfonylradical having l toabout 8 carbon atoms, or a phenylor substituted phenylsulfo nyl radicalhaving 6 to about 9 carbon'atoms;

with the proviso that there be no more than one sulfo radical and nomore than one carboxy radical present in said compound.

As mentioned above, the present compounds contain a carrier moiety (Can)which, as a function [direct or inverse) of oxidation under alkalineconditions, provides a substance having a mobility different than thatof the starting compound. Depending upon the carrier used, thedyeproviding compounds of this invention can be of two basic types: (1initially immobile compounds of which at least a portion is renderedmobile or diffusible as a function of development, or (2) initiallymobile or diffusible compounds which are rendered immobile as a functionof development. Carriers useful in initially immobile dye-providingcompounds such as those wherein the carrier, under alkaline conditions,effects a splitting off of a ballast group from the dye moiety aredescribed further in Whitmore Canadian Pat. No. 602,607, dated Aug. 2,1960, and Whitmore U.S. Pat. No. 3,227,552, issued Jan. 4 I966, bothincorporated herein by reference. Among the preferred initially immobilecompounds are those in which the carrier, as a function of oxidationunder alkaline conditions, releases a dye having a mobility differentthan that of the starting immobile compound. For example, usefulcarriers for compounds in which the carrier moiety undergoesintramolecular ring closure upon oxidation to split off a dye aredescribed in US. Pat. Nos. 3,443,939, 3,443,940 and 3,443,94l, allissued May I3, 1969, and' all incorporated herein by reference. Specialinitially immobile carriers useful in forming a diffusible substance asan inverse function of oxidation are described in copending Hinshaw andCondit application Ser. No. 326,628, filed Jan. 26, I973, and entitledPositive-Working lmmobile Photographic Compounds and PhotographicElements Containing Same", incorporated herein by reference. lmprovedinitially immobile dye-providing compounds which undergo redox reactionsfollowed by alkali cleavage of the carrier to split off a dye aredisclosed in Fleckenstein et al. Ser. No. 282,796, filed Aug. 22, [972,now abandoned, entitled Photographic Systems", incorporated herein byreference. The ballasted phenolic and naphtholic carriers ofFleckenstein ct al. are among preferred carrier moieties. Still otheruseful carriers are described in US. Pat. No. 3,628,952, is sued Dec. 21l97 l. Additionally, carriers useful in the formation of initiallymobile compounds such as those wherein the carrier functions as adeveloper are described in Friedman U.S. Pat. No. 2,543,69l, issued Feb.27, 1951-, US. Pat. No. 2,983,606, issued May 8, l96l; and US. Pat. No3,255,001, issued June 7, 1966; all incorporated herein by reference.Carriers of this latter type include various hydroquinone moieties.

Examples of bivalent alkylene linking groups representative of R are -CHC,H -C,-,H C H C,H,,, etc, as well as branched alkylenc radicals such asetc.

References hereinafter to o, m and p mean that either the ortho, meta orpara radicals are indicated, as the case may be.

Examples of phenylene and substituted phenylene radicals representativeof R are o,m,p-phenylene, o,m,p-phenylene substituted with chloro,methoxy, butoxy, bromo, cyano. nitro, methyl, ethyl, carboxy, sulfo,amino, etc.

As used herein the oxygenor sulfur-containing bivalent radicalsrepresentative of L are oxy (O), carbonyl (CO-), carboxamido (CONH),carbamoyl (NHCO-), sulfonamido (SO NH), sulfamoyl (NHSO sulfinyl (-S0)and sulfonyl (SO Therefore, non-limiting examples of bivalent linkinggroups which may be represented by X are etc.

Examples of the groups which R may represent are hydrogen, methyl,ethyl, isopropyl. pentyl, hexyl, etc. The alkyl group represented by Rmay additionally be substituted with cyano, hydroxy, methoxy, etc.

Examples of groups representative ofQ are a hydrogen atom, a hydroxyradical or a radical having the formula NHCOR or -NHSO R" wherein R isas described previously such as NHCOCH NH- COC H NHCOC H NHCOC H CN, NH-

Examples of the groups which G may represent are hydroxy, salts i.e., atrialkyl or tetralkyl ammonium salt (sometimes called amine salts")which does not adversely affect the photographic utility of the cyanimage dye-providing compound or the physical or chemical processes whichoccur during development of the image.

G may also advantageously represent a hydrolyzable acyloxy group havingthe formula wherein R is as described previously. Non-limiting examplesof these hydrolyzable groups are thereof such as alkali metal (e.g., O

etc; a carboxy radical including salts thereof, such as alkali metalsalts or photographically inactive ammonium salts (e.g., COOH, -COO Lfi,COO K COO Na COO NH em), a fluorosulfonyl radical (-SOJ), a SO C,,Hradical,

etc., a sulfo radical including salts thereof, such as alkali metal orphotographically inactive ammonium salts (mgr, s ,H, so 11 50, K SO:, NaS0 NHf, etc.)', SO,NH SO,NHCH SO NHC H SO N(CH SO NHCH C H T w r enPreferred compounds are those having Formulas l and ll above wherein: g

Car represents a carrier moiety which, as a function of oxidation underalkaline conditions, releases a dye having a mobility different thanthat of said compound;

R represents an alkylene radical having 1 to about 4 carbon atoms,phenylenc or phenylene substituted with carboxy, chloro, methyl ormethoxy;

L represents sulfamoyl, sulfonamido, carbamoyl or carboxamido;

R represents hydrogen;

q is an integer having a value of l;

m is an integer having a value of to 1;

Q represents hydrogen, hydroxy, NHCOR or NHSO R wherein R represents analkyl radical having 1 to about 4 carbon atoms; an alkyl radical havingI to about 4 carbon atoms substituted with hydroxy, cyano, sulfamoyl,carboxy or sulfo; benzyl, phenyl or phenyl substituted with carboxy,chloro, methyl, methoxy or sulfamoyl;

D represents chloro, fluoro, bromo, cyano, trifluoromethyl, nitro,fluorosulfonyl, alkylsulfonyl having 1 to about 6 carbon atoms,alkylsulfonyl having 1 to about 6 carbon atoms substituted with hydroxy,phenyl, cyano, sulfamoyl, carboxy, fluorosulfonyl or sulfo;phenylsulfonyl; phenylsulfonyl substituted with bydroxy, sulfamoyl,fluorosulfonyl, carboxy or sulfo; a sulfamoyl radical having the formulaSO NHR wherein R is hydrogen, an alkyl radical having l to about 4carbon atoms, or an alkyl radical having 1 to about 4 carbon atomssubstituted with hydroxy, cyano, sulfamoyl, carboxy or sulfo; benzyl,phenyl or phenyl substituted with hydroxy, sulfonyl, sulfamoyl, carboxyor sulfo; a carbamoyl radical having the formula CON(R wherein R ishydrogen or methyl, and

D can represent a substitutent having the formula Car[X(NRJ) or Car-X-J,provided that the Car[X-(NRJ) substituent on the naphthalene nucleus ofFormula I is replaced by an M group or the CarX-JNH substituent on thenaphthalene nucleus of Formula H is replaced by a Q group wherein Car,X, J, R, q and m are as described previously;

E represents hydrogen, fluoro, or chloro; and

M represents hydrogen or a sulfamoyl radical of the formula SO NHR"'wherein R is hydrogen; an alkyl radical of l to about 4 carbon atoms; analkyl radical having I to about 6 carbon atoms substituted with hydroxy,cyano, sulfamoyl, carboxy, or sulfo; benzyl, phenyl or phenylsubstituted with hydroxy, sulfamoyl, carboxy or sulfo.

Especially preferred compounds are those having Formulas l and ll abovewherein the Car-X- -.lNH- substitucnt in Formula ll is in the S-positionon the naphthalene nucleus relative to G; and the Car[X-(NR-J),,],,,--substituent in Formula I is in the 5- or fi-position on the naphthalenenucleus relative to G;

R represents an alkylene radical having l to about 4 carbon atoms, orphenylene;

L represents sulfamoyl or sulfonamido;

J represents sulfonyl;

Q is in the 8-position relative to G and represents hydrogen, hydroxy,-NHSO R or NHCOCH G represents hydroxy, a photographically inactiveammonium salt thereof, or a hydrolyzable acyloxy group having theformula:

wherein R is an alkyl radical having 1 to about 18 carbon atoms, phenylor phenyl substituted with chloro or nitro;

D represents chloro, bromo, cyano, trifluoromethyl, nitro, alkylsulfonylhaving 1 to about 6 carbon atoms, or benzylsulfonyl;

E represents hydrogen; and

M represents hydrogen.

Even more preferred compounds are those wherein X represents Grepresents hydroxy or a hydrolyzable acyloxy group; and

D represents an alkylsulfonyl radical having l to about 4 carbon atoms.

Even more especially preferred compounds are those having Formulas l andII above wherein Car represents a radical of the formula:

III.

NHSOaor SO NHBall. Examples of some preferred carriers are follows:

isrli w-t or fused directly to the benzene nucleus. etc. Useful ballastgroups generally have at least 8 carbon atoms such as a substituted orunsubstituted alkyl group of 8 or 22 carbon atoms. an amide radicalhaving 8 to 30 carbon atoms, a keto radical having 8 to 30 carbon atomsctc., and may even comprise a polymer backbone. Especially preferredcompounds are those wherein the ballast is attached to the benzenenucleus through a carbamoyl radical (NHCO) or a sulfamoyl radical (SONH) in which the nitrogen is adjacent the ballast group.

in addition to the ballast, the benzene nucleus in the above formula mayhave groups or atoms attached thereto such as the halogens, alkyl, aryl,alkoxy. aryloxy, nitro, amino, alkylamino, arylamino, amido, cyano,alkylmercapto, keto, carboalkoxy, bcterocyclic groups etc.

In a preferred embodiment of this invention CAR is a moiety which as afunction of oxidation under alkaline conditions, releases a dye having amobility different than that of the image dye-providing compounds.

The preferred novel dyes which are released from the carrier moieties asa function of oxidation under alkaline conditions may be represented bythe following formulas:

X, R, J, q, m. Q, G, M, D and E are as described previously, except thatthe Car substituents described for D are replaced by Z. The preferredreleased dyes. of course, correspond to the above mentioned preferredimage dye-providing compounds set forth above.

When Z represents SO H the dyes thus represented may be released by thereactions described in Bloom, U.S. Pat. No. 3.443940 in Puschel, U.SiPat. No. 31128952 and Gompf, US. Pat. No. 1698.897. When Z representslower alkyl-NH- (i.e., an alkyl group having l to about 4 carbon atoms),the dyes thus represented may be released by the reactions described inHinshaw et al., U.S. Ser. No. 326,628. The especially preferred releaseddyes of our invention are those represented by Formulas IV and V abovewhen Z represents -SO NH. These dyes may be released by the reactionsdescribed in Fleckenstein et al., allowed Ser. No. 351,763, acontinuation-in-part of U.S. Ser. No. 282,796 from the carrier moietiesdescribed by Formula ill.

A suitable process for producing a photographic transfer image in colorusing the compounds of our invention, for example those wherein Car isas shown in Formula 111, comprises the steps of:

l. treating the above-described photosensitive element with an alkalineprocessing composition in the presence of a silver halide developingagent to effect development of each of the exposed silver halideemulsion layers, thereby oxidizing the developing agent and the oxidizeddeveloping agent in turn cross-oxidizing the sulfonamido compound;

2. forming an imagewise distribution of diffusible released dye as afunction of the imagewise exposure of each of the silver halide emulsionlayers by cleaving each cross-oxidized sulfonamido compound; and

3. diffusing to a dye image-receiving layer at least a portion of eachof the imagewise distributions of diffusible released dye to provide animage.

The photosensitive element in the above-described process can be treatedwith an alkaline processing composition to effect or initiatedevelopment in any manner. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in oursystem contains the developing agent for development, although thecomposition could also just be an alkaline solution where the developeris incorporated in the photosensitive element, in which case thealkaline solution serves to activate the incorporated developer.

A photographic film unit according to our invention which is adapted tobe processed by passing the unit between a pair of juxtaposedpressure-applying members, comprises:

1. a photosensitive element as described above;

2. a dye image-receiving layer; and

3. means for discharging an alkaline processing composition within thefilm unit such as a rupturable container which is adapted to bepositioned during processing of the film unit so that a compressiveforce applied to the container by the pressure applying members willeffect a discharge of the contents of the container within the filmunit;

the film unit containing a silver halide developing agent.

The dye image-receiving layer in the above-described film unit can belocated on a separate support adapted to be superposed on thephotosensitive element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in US. Pat. 3,362,819.When the means for discharging the processing composition is arupturable container, typically it is positioned in relation to thephotosensitive element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as found in a camera designed for incamera processing, will effecta discharge of the con tents of the container between theimage-receiving element and the outermost layer of the photosensitiveelement. After processing, the dye image-receiving element is separatedfrom the photosensitive element.

The dye image-receiving layer in the above-described film unit can alsobe located integral with the photosensitive silver halide emulsionlayer. One useful format for integral receiver-negative photosensitiveelements is disclosed in Belgian Patent 757,960. In such an embodiment,the support for the photosensitive element is transparent and is coatedwith an image-receiving layer, a substantially opaque light reflectivelayer, e.g., TiO and then the photosensitive layer of layers describedabove. After exposure of the photosensitive element, a rupturablecontainer containing an alkaline processing composition and an opaqueprocess sheet are brought into superposed position. Pressure-applyingmembers in the camera rupture the container and spread processingcomposition over the-photosensitive element as the film unit iswithdrawn from the camera. The processing composition develops eachexposed silver halide emulsion layer and dye images are formed as afunction of development which diffuse to the im age-receiving layer toprovide a position, right-reading image which is viewed through thetransparent support on the opaque reflecting layer background,

Another format for integral negative-receiver photosensitive elements inwhich the present invention can be employed is disclosed in BelgianPatent 757,959. In this embodiment, the support for the photosensitiveelement is transparent and is coated with the imagereceiving layer, asubstantially opaque, light-reflective layer and the photosensitivelayer or layers described above. A rupturable container containing analkaline processing composition and an opacifier is positioned adjacentto the top layer and a transparent top sheet. The film unit is placed ina camera, exposed through the transparent top sheet and then passedthrough a pair of pressure-applying members in the camera as it is beingremoved therefrom. The pressure-applying members rupture the containerand spread processing composition and opacifier over the negativeportion of the film unit to render it light insensitive. The processingcomposition develops each silver halide layer and dye images are formedas a result of development which diffuse to the image-receiving layer toprovide a rightreading image that is viewed through the transparentsupport on the opaque reflecting layer background.

Still other useful integral formats in which our sulfonamido compoundscan be employed are described in U.S. Pat. 3,415,644; 3,415,645;3,415,646; 3,647,437; and 3,635,707.

The film unit or assembly of the present invention can be used toproduce positive images in single or multicolors. In a three-colorsystem, each silver halide emulsion layer of the film assembly will haveassociated therewith an image dye-providing material possessing apredominant spectral absorption within the region of the visiblespectrum to which said silver halide emulsion is sensitive, i.e., theblue-sensitive silver halide emulsion layer will have a yellow imagedye-providing material associated therewith, the green-sensitive silverhalide emulsion layer will have a magenta image dyeproviding materialassociated therewith, and the redsensitive silver halide emulsion layerwill have a cyan image dye-providing material associated therewith. Theimage dye-providing material associated with each silver halide emulsionlayer can be contained either in the silver halide emulsion layer itselfor in a layer contiguous to the silver halide emulsion layer. The cyanimage dye-providing material will, of course, be a compound of thisinvention.

when G is a hydrolyzable acyloxy group, the absorption spectrum of theazo dye is shifted to shorter wavelength. Shifted dyes" of this typeabsorb light outside the range to which the associated silver halidelayer is sensitive. The use of certain related shifted azo dyedevelopers is described in U.S. Pat. 3,307,947 issued Mar. 7, 1967. Theshifted dye-providing materials of this invention can be advantageouslycontained in the silver halide emulsion layer without substantiallyreducing the sensitivity of the layer. The acyloxy group is hydrolyzedby the alkaline processing composition, releasing the cyan dye of thedesired hue. The yellow and magenta image dye-providing materials can beselected from a variety of materials such as those compounds describedby Fleckenstein et al. U.S. Ser. No. 282.796, mentioned previously.Additional useful magenta image dye-providing materials are described inco-filed Haase et al. application Ser. No. 331,729, and now abandoned,entitled Novel Compounds and Photographic Materials".

The concentration of the compounds, which preferably arealkali-cleavable upon oxidation, that are employed in the presentinvention can be varied over a wide range depending upon the particularcompound employed and the results which are desired. For example, theimage dye-providing compounds of the present invention can be coated inlayers as dispersions in a hydrophilic film-forming natural or syntheticpolymer, such as gelatin, polyvinyl alcohol, etc., which is adapted tobe permeated by aqueous alkaline processing composition. Preferably, theratio of dye-providing compound to polymer will be about 0.25 to about4.0. The present compounds may then be incorporated in a gelatin bytechniques known in the art (e.g., a high boiling, water immiscibleorganic solvent or a low boiling or water miscible organic solvent).

Depending upon which Car is used on the present compounds, a variety ofsilver halide developing agents can be employed in our invention. If thecarrier used is that of Formula iii, any silver halide developing agentcan be used as long as it cross-oxidizes with the image dye-providingcompounds used herein. The developer can be employed in thephotosensitive element to be activated by the alkaline processingcomposition. Specific examples of developers which can be employed inour invention include hydroquinone, aminophenols, e.g.,N-methylaminophenol, Phenidone (i-phenyl-3- pyrazolidone) trademark ofllford, Ltd.; Dimezone (i-phenyl-4,4-dimethyl-3-pyrazolidone) trademarkof Eastman Kodak Company; i-phenyl4-methyl-4-hydroxymethyl-3-pyrazolidone, N,N-diethyl-pphenylenediamine.3-methyl-N,N-diethyl-pphenylenediamine,3-methoxy-N,N-diethyl-pphenylenediamine, etc. The black-and-whitedevelopers in this list are preferred, in that they have a reducedpropensity of staining the dye image-receiving layer.

In a preferred embodiment of our invention, the

silver halide developer in our process becomes oxidized upon developmentand reduces silver halide to silver metal. The oxidized developer thencross-oxidizes the sulfonamido-phenol or sulfonamido-naphtholdyereleasing compound. The product of cross-oxidation then undergoesalkaline hydrolysis, thus releasing an imagewise distribution ofdiffusible anionic dye which then diffuses to the receiving layer toprovide the dye image. the diffusible moiety is transferable in alkalineprocessing composition either by virtue of its self-dii fusivity or byhaving attached to it one or more solubilizing groups such as --COOH,-SO H, --SO,NRR, H. etc. (where R and R" are as described previouslywith at least one being hydrogen).

in using the especially preferred dye releasing compounds according toour invention. the production of diffusibie dye images is a function ofdevelopment of the silver halide emulsions with a silver halidedeveloping agent to form either negative or direct positive silverimages in the emulsion layers. If the silver halide emulsion employedforms a direct positive silver image, such a direct positiveinternal-image emulsion or a solarizing emulsion, which develops inunexposed ar cas, a positive image can be obtained on the dyeimagereceiving layer. After exposure of the film unit, the alkalineprocessing composition permeates the various layers to initiatedevelopment in the unexposed photosensitive silver halide emulsionlayers. The developing agent present in the film unit develops each ofthe silver halide emulsion layers in the unexposed areas (since thesilver halide emulsions are direct-positive ones), thus causing thedeveloping agent to become oxidized imagewise corresponding to theunexposed areas of the direct-positive silver halide emulsion layers.The oxidized developing agent then cross-oxidizes the dyereleasingcompounds and the oxidized form ofthe compounds then undergoes abase-catalyzed reaction in a preferred embodiment of our invention, torelease the preformed dyes imagewise as a function of the imagewiseexposure of each of the silver halide emulsion layers. At least aportion ofthe imagewise distributions of diffusible dyes diffuse to theimage-receiving layer to form a positive image of the original subject.After being contacted by the alkaline processing composition, apH-lowering layer in the film unit lowers the pH of the film unit (orthe image-receiving unit) to stabi lize the image.

Internal-image silver halide emulsions useful in those embodimentswherein a dye is released as a function of oxidation are direct-positiveemulsions that form latent images predominantly inside the silver halidegrains, as distinguished from silver halide grains that form latentimages predominantly on the surface thereof. Such internal-imageemulsions are described by Davey at a]. in U.S. Pat. 2,592,250, issuedApr. 8, i952, and elsewhere in the literature. Other useful emulsionsare described in U.S. Pat. No. 3,761,276, dated September 25, 1973.Internal-image silver halide emulsions can be defined in terms of theincreased maximum density obtained when developed with internal-typedevelopers over that obtained when developed with surface-type"developers. Suitable internal-image emulsions are those which, whenmeasured according to normal photographic techniques by coating a testportion of the silver halide emulsion on a transparent support, exposingto a light-intensity scale having a fixed time between 0.0i and isecond, and developing for 3 minutes at 20C. in Developer A below(internaltype" developer), have a maximum density at least five timesthe maximum density obtained when an equally exposed silver halideemulsion is developed for 4 minutes at 20C. in Developer described below("surface-type developer). Preferably, the maximum density in DeveloperA is at least 0.5 density unit greater than the maximum density inDeveloper B.

DEVELOPER B P-hydroxyphenylglycine Sodium carbonate Water in make oneliter.

m g. g.

The internal-image silver halide emulsions when processed in thepresence of fogging or nucleating agents provide direct positive silverimages. Such emulsions are particularly useful in the above-describedembodiment. Suitable fogging agents include the hydrazines disclosed inlves U.S. Pat. 2,588,982 issued Mar. 11, 1952, and 2,563,785 issued Aug.7, 1951; the hydrazides and hydrazones disclosed in Whitmore U.S. Pat.3,227,552 issued Jan. 4, 1966; hydrazone quaternary salts described inLincoln and Heseltine U.S. Pat. 3,615,615 issued Oct. 26, 1971;hydrazone containing polymethine dyes described in Spence and JanssenU.S. Pat. 3,718,470 issued Feb. 27, 1973; or mixtures thereof. Thequantity of fogging agent employed can be widely varied depending uponthe results desired. Generally, the concentration of fogging agent isfrom about 0.4 to about 8 grams per mole of silver in the photosensitivelayer in the photosensitive element or from about 0.1 to about 2 gramsper liter of developer if it is located in the developer. The foggingagents described in U.S. Pat. Nos. 3,615,615 and 3,718,470, however, arepreferably used in concentrations of about 0.5 to 10.0 milligrams permole of silver in the photosensitive layer.

The solarizing direct-positive silver halide emulsions useful in theabove-described embodiment are wellknown silver halide emulsions whichhave been effectively fogged either chemically, such as by the use ofreducing agents, or by radiation to a point which correspondsapproximately to the maximum density of the reversal curve as shown byMees, The Theory of the Photographic Process, published by the MacmillanCo., New York, New York, 1942, pages 261-297. Typical methods for thepreparation of solarizing emulsions are shown by Groves British Patent443,245, Feb. 25, 1936, who subjected emulsions to Roentgen rays untilan emulsion layer formed therefrom, when developed without preliminaryexposure, is blackened up to the apex of its graduation curve; SzazBritish Patent 462,730, Mar. 15, 1937, the use of either light orchemicals such as silver nitrate, to convert ordinary silver halideemulsions to solarizing direct positive emulsions; and Arens U.S. Pat.2,005,837, June 25, 1935, the use of silver nitrate and other compoundsin conjunction with heat to effect solarization. Particularly useful arethe fogged direct-positive emulsions of Berriman U.S. Pat. 3,367,778;lllingsworth U.S. Pat. 3,501,305, 3,501,306 and 3,501,307; andcombinations thereof.

Other embodiments in which our imaging chemistry can be employed includethe techniques described in U.S. Pat. Nos. 3,227,550, 3,227,551,3,227,552 and 3,364,022.

lf photographic elements are used which contain compounds of thisinvention wherein Car is a silver halide developer as described, forexample, in U.S. Pat. No. 2,983,606, when the liquid processingcomposition is applied, it permeates the emulsion to provide a solutionof the dye developer substantially uniformly distributed in theemulsion. As the exposed silver halide emulsion is developed to anegative silver image, the oxidation product of the dye developer isimmobilized or precipitated in situ with the developed silver, therebyproviding an imagewise distribution of unoxidized dye developerdissolved in the liquid processing composition. This immobilization isapparently due, at

18 least in part, to a change in the solubility characteristics of thedye developer upon oxidation. At least part of this imagewisedistribution of unoxidized dyedeveloper is transferred to a superposedimage-receiving layer to provide a transfer image.

Negative silver halide emulsions useful in certain embodiments of thisinvention, such as the above, can comprise, for example, silverchloride, silver bromide, silver chlorobromide, silver bromoiodide,silver chlorobromiodide or mixtures thereof. The emulsions can becoarseor fine-grain and can be prepared by any of the well-knownprocedures, e.g., single-jet emulsions such as those described inTrivelli and Smith, The Photographic Journal, Vol. LXXlX, May, 1939 (PP.330-338), double-jet emulsions, such as Lippmann emulsions, ammoniacalemulsions, thiocyanate or thioether ripened emulsions such as thosedescribed in Nietz et al. U.S. Pat. 2,222,264 issued Nov. 19, 1940;lllingsworth U.S. Pat. 3,320,069 issued May 16. 1967; and Jones U.S.Pat. 3,574,628 issued Apr. 13, 1971. The emulsions may be monodispersedregular-grain emulsions such as the type described in Klein and Moisar,J. Phot. Sci., Vol. 12, No. 5, Sept/Oct, 1964 (pp. 242-251).

Another embodiment of our invention uses the image-reversing techniquedisclosed in British Patent 904,364, page 19, lines l-4l. In this systemour dyeproviding compounds are used in combination with physicaldevelopment nuclei in a nuclei layer contiguous to the photosensitivesilver halide negative emulsion layer. The Film unit contains a silverhalide solvent, preferably in a rupturable container with the alkalineprocessing composition.

The various silver halide emulsion layers of a color film assembly ofthe invention can be disposed in the usual order, i.e., theblue-sensitive silver halide em ulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a yellowcolloidal silver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layer for absorbing or filteringblue radiation that may be transmitted through the blue-sensitive layer.If desired, the selectivity sensitized silver halide emulsion layers canbe disposed in a different order, e.g., the blue-sensitive layer firstwith respect to the exposure side, followed by the red-sensitive andgreensensitive layers.

The rupturable container employed in this invention can be of the typedisclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 2,653,732; 2,724,051;3,056,492; 3,056,491 and 3,152,515. In general, such containers comprisea rectangular sheet of fluidand air-impervious material foldedlongitudinally upon itself to form two walls which are sealed to oneanother along their longitudinal and end margins to form a cavity inwhich processing solution is contained.

In a color film unit according to this invention, each silver halideemulsion layer containing a dye imageproviding material or having thedye image-providing material present in a contiguous layer may beseparated from the other silver halide emulsion layers in theimage-forming portion of the film unit by materials including gelatin,calcium alginate, or any of those disl9 closed in U.S. Pat. No.3.384.483. polymeric materials such as polyvinylamides as disclosed inU.S. Pat. 3.421.892. or any of those disclosed in French Patent2.028.236 or U.S. Pat. Nos. 2.992.104; 3.043.692; 3.044.873; 3.061.428;3.069.263; 3.069.264; 3.121.011; and 3.427.158.

Generally speaking. except where noted otherwise, the silver halideemulsion layers in the invention comprise photosensitive silver halidedispersed in gelatin and are about 0.6 to 6 microns in thickness; thedye image-providing materials are dispersed in an aqueous alkalinesolution-permeable polymeric binder. such as gelatin. as a separatelayer about 1 to 7 microns in thickness; and the alkalinesolution-permeable polymeric interlayers. e.g.. gelatin. are about 1 to5 microns in thickness. Of course. these thicknesses are approximateonly and can be modified according to the product desired.

Any material can be employed as the image-receiving layer in thisinvention as long as the desired function of mordanting or otherwisefixing the dye images will be obtained. The particular material chosenwill. of course. depend upon the dye to be mordanted. If acid dyes areto be mordanted. the image-receiving layer can contain basic polymericmordants such as polymers of amino guanidine derivatives of vinyl methylketone such as described in Minsk U.S. Pat. 2.882.156. issued Apr. 14.1959. and basic polymeric mordants such as described in Cohen et al.U.S. Pat. No. 3.625.694. issued Dec. 7, 1971; U.S. Pat. No. 3.709.690.issued Jan. 9. 1973; and US. application Ser. No. 400.778. filed Sept.26. 1973. and now US. Pat. 3.898.088. See also U.S. application Ser. No.412.992 of Burness et al.. filed Nov. 5. 1973. and now U.S. Pat.3.859.096.

Preferred mordants are cationic mordants such as polymeric compoundscomposed of a polymer having quaternary nitrogen groups and at least twoaromatic nuclei for each quaternary nitrogen in the polymer cation (ie.having at least two aromatic nuclei for each positively charged nitrogenatom). such polymeric compounds being substantially free of carboxygroups. Useful mordants of this type are comprised of units of thefollowing formula in copolymerized relationship with units of at leastone other ethylenically unsaturated monomer:

wherein R and R" each represent a hydrogen atom or a lower alkyl radical(of l to about 6 carbon atoms) and R" can additionally be a groupcontaining at least one aromatic nucleus (cg. phenyl. naphthyl. tolyl);Q can be a divalent alkylene radical (of l to about 6 carbon atoms). adivalent arylene radical, a divalent aralkylenc radical. a divalentarylenealkylene radical. such as group; R. R and R can be alkyl. aralkylor aryl. or R" and R'" and the nitrogen atom to which they are attachedcan together with Q represent the atoms and bonds necessary to form aquaternized nitrogen-containing heterocyclic ring. and X is a monovalentnegative salbforming radical or atom in ionic relationship with thepositive salt-forming radical. wherein said polymer is substantiallyfree of carboxy groups and wherein the positive salt forming radical ofsaid poly mer comprises at least two aryl groups for each quaternarynitrogen atom in said polymer. In .ie preferred embodiment, Q representsa phenylene or substituted phenylene radical and R. R and R" are thesame or different and represent alkyl groups. the sum of their carbonatoms exceeding 12. These preferred polymeric cationic mordants aredescribed further in the abovementioned U.S. Pat. No. 3.709.690 and US.application Ser. No. 400.778. incorporated herein by reference.

Other mordants useful in our invention include poly- 4 vinylpyridine.the 2-vinyl pyridine polymer methyl-ptoluene sulfonate and similarcompounds described in Sprague et al. US. Pat. 2.484.430. issued Oct.11. 1949, and cetyl trimethylammonium bromide. etc. Effective mordantingcompositions are also described in Whitmore U.S. Pat. 3.271.148 and BushU.S. Pat. 3.271.147. both issued Sept. 6. 1966.

Generally, good results are obtained when the imagereceiving layer.preferably alkaline solution-permeable. is transparent and about 0.25 toabout 0.40 mil in thickness. This thickness. of course. can be modifieddepending upon the result desired. The image-receiving layer can alsocontain ultraviolet absorbing materials to protect the mordanted dyeimages from fading due to ultraviolet light. brightening agents such asthe stilbenes. coumarins. triazines. oxazoles. dye stabilizers such asthe chromanols. alkylphenols. etc.

Use of a pH-lowering material in the dye image receiving element ofafilm u nit according to the invention will usually increase thestability of the transferred image. Generally, the pH-lowering materialwill effect a reduction in the pH ofthe image layer from about 13 or 14to at least 11 and preferably 4-8 within a short time after imbibition.For example. polymeric acids as disclosed in U.S. Pat. 3,362,819. orsolid acids or metallic salts. e.g.. zine acetate. zinc sulfate.magnesium acetate. etc. as disclosed in U.S. Pat. 2.584.030 may beemployed with good results. Such pH-lowering materials reduce the pH ofthe film unit after developnent to terminate development andsubstantially reduce further dye transfer and thus stabilize the dyeimage.

An inert timing or spacer layer car be employed in the practice of ourinvention over the pl owering layer which times" or controls the pHTCdlJkilUl'l as a function of the rate at which alkali diffuses throughthe inert spacer layer. Examples of such timing layers in clude gelatin,polyvinyl alcohol or any of those disclosed in U.S. Pat. 3,455,686. Thetiming layer may be effective in evening out the various reaction ratesover a wide range of temperatures, e.g., premature pH reduction isprevented when imbibition is effected at temperatures above roomtemperature, for example, at 95100F. The timing layer is usually about0.1 to about 0.7 mil in thickness. Especially good results are obtainedwhen the timing layer comprises a hydrolyzable polymer or a mixture ofsuch polymers which are slowly hydrolyzed by the processing composition.Examples of such hydrolyzable polymers include polyvinyl acetate,polyamides, cellulose esters, etc.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., sodiumhydroxide, sodium carbonate or an amine such as diethylamine, preferablypossessing a pH in excess of l l, and preferably containing a developingagent as described previously. The solution also preferably contains aviscosity-increasing compound such as a high-molecular-weight polymer,e.g., a water-soluble ether inert to alkaline solutions such ashydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulosesuch as sodium carboxymethyl cellulose. A concentration ofviscosity-increasing compound of about 1 to about 5% by weight of theprocessing composition is preferred which will impart thereto aviscosity of about 100 cp. to about 200,000 cp. in certain embodimentsof our invention, an opacifying agent, e.g., TiO carbon black, pHindicator dyes, etc., may be added to the processing composition.

While the alkaline processing composition used in this invention can beemployed in a rupturable container, as described previously, toconveniently facilitate the introduction of processing composition intothe film unit, other methods of inserting processing composition intothe film unit could also be employed, e.g., interjecting processingsolution with communicating members similar to hypodermic syringes whichare attached either to a camera or camera cartridge.

The alkaline solution-permeable, substantially opaque, light'reflectivelayer employed in certain embodiments of photographic film units of ourinvention can generally comprise any opacifler dispersed in a binder aslong as it has the desired properties. Particularly desirable are whitelight-reflective layers since they would be esthetically pleasingbackgrounds on which to view a transferred dye image and would alsopossess the optical properties desired for reflection of incidentradiation. Suitable opacifying agents include titanium dioxide, bariumsulfate, zinc oxide, barium stearate, silver flake, silicates, alumina,zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate,kaolin, mica, or mixtures thereof in widely varying amounts dependingupon the degree of opacity desired. The opacifying agents may bedispersed in any binder such as an alkaline solution-permeable polymericmatrix such as, for example, gelatin, polyvinyl alcohol, and the like.Brightening agents such as the stilbenes, coumarins, triazines andoxazoles can also be added to the light-reflective layer, if desired.When it is desired to increase the opacifying capacity of thelight-reflective layer, dark-colored opacifying agents, cg, carbonblack, nigrosine dyes, etc., may be added to it, or coated in a separatelayer adjacent to the light-reflective layer.

The supports for the photographic elements of this invention can be anymaterial as long as it does not deleteriously effect the photographicproperties of the film unit and is dimensionally stable. Typicalflexible sheet materials include cellulose nitrate film, celluloseacetate film, poly(vinyl acetal) film, polystyrene film,poly(cthyleneterephthalate) film, polycarbonate film, poly-a'olefinssuch as polyethylene andpolypropylene film, and related films orresinous materials. The support can be from about 2 to about 9 mils inthickness.

The silver halide emulsions useful in our invention are well known tothose skilled in the art and are described in Product Licensing Index,Vol. 92, Dec, 1971, publication 9232, p. 107, paragraph I, Emulsiontypes"; they may be chemically and spectrally sensitized as described onpage 107, paragraph lll, Chemical sensitization", and pp. 108-109,paragraph XV, Spectral sensitization, of the above article; they can beprotected against the production of fog and can be stabilized againstloss of sensitivity during keeping by employing the materials describedon p. 107, paragraph V, Antifoggants and stabilizers, of the abovearticle; they can contain development modifiers, hardeners, and coatingaids as described on pp. 107-108, paragraph 1V, Development modifiers";paragraph V11, Hardeners"; and paragraph XI], Coating aids", of theabove article; they and other layers in the photographic elements usedin this invention can contain plasticizers, vehicles and filter dyesdescribed on p. 108, paragraph Xi, Plasticizers and lubricants, andparagraph V111, Vehicles, and p. 109, paragraph XVI, Absorbing andfilter dyes", of the above article; they and other layers in thephotographic elements used in this invention may contain addenda whichare incorporated by using the procedures described on p. 109, paragraphXVII, Methods of addition", of the above article; and they can be coatedby using the various techniques described on p. 109, paragraph XVlll,Coating procedures", of the above article, the disclosures of which arehereby incorporated by referonce.

it will be appreciated that there remains in the photographic elementafter transfer has taken place an imagewise distribution of dye inaddition to developed silver. A color image comprising residualnondiffusible compound may be obtained in this element if the residualsilver and silver halide are removed by any conventional manner wellknown to those skilled in the photographic art, such as a bleach bathfollowed by a fix bath, a bleach-fix bath, etc. The imagewiscdistribution of dye may also diffuse out of the element into thesebaths, if desired, rather than to an image-receiving element. if anegative-working silver halide emulsion is employed in suchphotosensitive element, then a positive color image, such as a colortransparency or motion-picture film, may be produced in this manner. Ifa direct-positive silver halide emulsion is employed in suchphotosensitive element, then a negative color image may be produced.

Preferably, when the desired dye image is retained in the image-formingunit, the image dye-providing materials are shifted (G is hydrolyzableacyloxy) and are incorporated in the silver halide emulsion layer.lmproved processes are described in U.S. Ser. No. 422,390, filed Dec. 6,1973.

The following examples are provided for a further understanding of theinvention. The structures of all of the compounds were confirmed bytheir infrared and EXAMPLE 1 Preparation of Compound No. l

A mixture of3.05 g. (0.0065 mol) of-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfonyl chloride and 3.2g. (0.0065 mol) of 4-amino-N-[4- (2,4-di-t-pentylphenoxy )-butyl]- l-hydroxy-2-naphthamide in 75 ml. of tetrahydrofuran under nitrogen wasstirred with 4.5 ml. of pyridine at room temperature for 90 minutes. Thesolid, precipitated by dilution with 500 ml. with hexane, was collectedon a filter funnel and dried to yield 4.8 g. (80%). The solid waspurified by dissolving the soluble material in tetrahydrofuran andreprecipitating with hexane. The still slightly impure solid waschromatographed on silica gel, the product being eluted withtetrahydrofuran. The eluents were concentrated and the solidprecipitated with hexane. The yield was 2.2 g. (37%), m.p. l70-3C.

PREPARATION OF lNTERMEDlATES a. The5-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfonylchloride was prepared from the sodium salt of the acid withchlorosulfonic acid: 3.55 g. (0.0075 mol) of sodium S-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfonate in 35 ml.of chlorosulfonic acid was heated at 60C. for l hour. The solution wascooled and poured onto ice. The solid was collected on a filter funneland dried in a vacuum desiccator to yield 2.8 g. (80%) of the productwhich contained a small amount of starting material.

b. The sodium 5-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfonate was prepared by the followingdiazotization and coupling reactions. To a solution of 55.8 g. (0.25mol) of l-amino-o-naphthalenesulfonic acid in 100 ml. of watercontaining 10 g. (0.25 mol) of sodium hydroxide was added 17.3 g. (0.25mol) of sodium nitrite in 50 ml. of water. At 05C., a dilute solution ofsulfuric acid, formed by adding 50 g. of ice to I25 ml. of concentratedsulfuric acid was added dropwise. After 1 hour, the solution was pouredinto a 3 liter flask and slowly heated to reflux (gas evolved at70-9()C.). The solution was heated at reflux for l /3 hours, cooled, pHadjusted to 7 using 50% sodium hydroxide, and an additional 425 g. of50% sodium hydroxide was added (Solution A). l7.3 g. (0.25 mol) ofsodium nitrite was added portionwise to 150 ml. of concentrated sulfuricacid at 0C. The mixture was allowed to warm to 70C., cooled to lOC., and54 g. (0.25 mol) of 2-amino5-nitrophenyl methyl sulfone was added. Themixture was stirred for ninety minutes and poured onto 625 g. ofice. Themixture was filtered and the filtrates kept (Solution B). Solution B wasadded to Solution A at 30C. After the addition, the pH was adjusted to 5and the mixture stirred for one-half hour. The solid was collected on afilter funnel, reslurried in water. After collecting the solid on afilter funnel and drying, the yield of product was g. (72%).

EXAMPLE 2 Preparation of Compound No. 2

To amixture of4.2 g. (0.009 mol) of 5-hydroxy-8-(2-methylsulfonyl-4nitrophenylazo)-l-naphthalenesulfonyl chloride and 4.4g. (0.009 mol) of 4-amino-N-[4-(2,4-di-t-pentylphenoxy)-butyl]-l-hydroxy-2-naphthamide in ml. oftetrahydrofuran under nitrogen. was added 4.5 ml. of pyridine. Thesolution was stirred at room temperature for two hours, and diluted to800 ml. with hexane. The solid was collected on a filter funnel anddried to yield 4.8 g. (58%) of crude product. The solid wasehromatographed on a silica column, using tetrahydrofuran to elute thedesired product. Concentration of the eluents yielded 3.2 g. of slightlyimpure solid. After twice suspending the solid in 200 ml. of chloroformand diluting with 400 ml. of hexane, the yield of purified product was2.4 g. (29%), m.p. -6C. dec.

PREPARATION OF INTERMEDIATES a. The5-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-l -naphthalenesulfonylchloride was prepared from the corresponding sodium sulfonate. 23.9 g.(0.05 mol) of sodium 5-hydroxy-8-(Z-methylsulfonyl-4-nitrophenylazo)-l-naphthalenesulfonate in l50 ml. of chlorosulfonicacid was heated at 65C. for l hour. The mixture was cooled and pouredonto ice. The mixture was kept at 5C. by addition of ice untilfiltration was complete. The solid was collected on a filter funnel anddried in a vacuum desiccator to yield 18.4 g. (78%). The solid wasdissolved in [50 ml. of tetrahydrofuran and diluted with 600 ml. ofchloroform. The solid that precipitated was collected on a filter funneland discarded. The filtrates were chromatographed on a silica column,with chloroform being used to elute the product. The chloroform eluentswere concentrated to dryness to yield 5.4 g. (23%) of purified product.

b. The sodium 5-hydroxy-8-(2-methylsulfonyl-4-nitrophenylazo)-l-naphthalenesulfonate was prepared using the methodshown in Example I by substituting a solution of l-naphthol-5'sulfonicacid in dilute sodium hydroxide for solution A. The yield was 100%.

c. 4-amino-N-[4-(2,4-di-t-pentylphenoxy)-butyl]-l hydrOxy-Z-naphthamidemay be prepared as follows: 1-hydroxy-N-[4-( 2,4-di-t-pentylphenoxy)-butyl }-2- naphthamide (US. Pat. 2,474,293) is coupled with adiazotized p-anisidine (eg.

EXAMPLE 3 Preparation of Compound No. 3

26 slowly at 10C. a solution formed by adding 17.3 g. (0.25 mol) ofsodium nitrite to a concentrated sulfuric acid at 10C., warming to 70C.to effect solution, and cooling to 20C. After the addition. 125 ml. ofthe propionic-acetic acid mixture in 50 g. of ice was added. Thesolution was stirred for two hours at ll5C., urea added to scavengeexcess nitrite. After stirring for 30 minutes. the mixture was filteredto remove starting material and the filtrates taken as Solution B.Solution B was added dropwise to Solution A at -l0 to C. The mixture wasstirred for thirty minutes, solid collected on a filter funnel and driedto yield 148 g. (125%) of material containing salts which are readilyremoved in subsequent steps.

EXAMPLE 4 Preparation of Compound No. 4

This compound was prepared in a manner similar to Example 1. After onerecrystallization from ethyl acetate, the yield was 46%, m.p. l624C.dec.

PREPARATION OF INTERMEDIATES a. 5-Hydroxy-8-(2chloro-4,6-dinitrophenylazo)-2- naphthalenesulfonyl chloride: 9.5 g.(0.02 mol) of sodium 5-hydroxy-8-(2-chloro-4,6-dinitrophenylazo)-2-naphthalenesulfonate was added portionwise to ml. of chlorosulfonicacid. 20 ml. of thionyl chloride was added and the mixture heated at60C. for 30 minutes. The solution was cooled, poured onto ice, andfiltered. The wet solid was dissolved in 800 ml. of CHCI; and dried withmagnesium sulfate. The mixture was filtered to remove the magnesiumsulfate, filtrates concentrated to dryness. The resulting solid wasslurried in hexane, collected on a filter funnel and dried to yield 6.7g. (71%). N0 impurities could be detected by thinlayer chromatography.

b. Sodium5-hydroxy-8-(2-chloro-4,6-dinitrophenylazo)-2maphthalenesulfonate: 55.8g. (0.25 mol) of l-amino-o-naphthalenesulfonic acid was dissolved in 100ml. of water containing 10 g. (0.25 mol) of sodium hydroxide. To thissolution was added 17.3 g. (0.25 mol) of sodium nitrite in 50 ml. ofwater. At 0 to 5C. this was added dropwise to a dilute solution ofsulfuric acid, formed by adding 50 g. of ice to 125 ml. of concentratedsulfuric acid. After one hour, the solution was poured into a 3 literflask and slowly heated to reflux (gas evolved at 7090C.). The solutionwas heated at reflux for 1% hours, cooled (Solution A). To 125 ml. of amixture of 2 parts propionic to 5 parts acetic acids containing drops ofTriton X-lOO (trademark of Rohm & Haas Company for a nonionic isooctylphenol polyethoxy ethanol dispersing agent) was added 66 g. of 82% solid2-chloro-4,6-dinitroaniline as a fine powder. The mixture was stirredfor 1V2 hours at room temperature then at 40C. for 1 hour. The mixturewas cooled to 0C. and to it was added EXAMPLE 5 Preparation of CompoundNo. 5

This compound was prepared in a manner similar to that used inExample 1. The yield was 23%, mp. l53-6C. dee. The5-hydroxy-8-(4-nitro-2-tri fluoromethylphenylazo)-2-naphthalenesulfonylchloride for use in this reaction was prepared using the methodexplained in Example 1. The yield was The sodium5-hydroxy-8-(4-nitr0-2-trifluoromethyl phenylazo)-2-naphthalenesulfonatewas prepared in a manner similar to that used in Example 1 The apparentyield was 107%. due to the presence of salt. It was used withoutpurification in the preparation of the acid chloride.

27 28 EXAMPLE 6 Preparation of Compound No. 6 This compound was preparedin a manner similar to SQZCHJ that used in Example I. The yield was 16/1, mp. 0-0 2489C. dec. The 4-bu1yramido-5-hydroxy-8-(2- N-N HO O Omethylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfo- .4 nyl chloride wasprepared by the method explained in O,' Example 3. The yield was 86%.The 4hutyramido-5 O hydroxy-8-(Z-methylsulfonyl-4-nitrophenylazo)-2- 3naphthalenesulfonic acid was prepared by a method l similar to that usedin Example 6. r/ )\T ,t --t,oNH-(cH2) 40- p --c5H11-+ 5H CgH'l 1-1EXAMPLE 8 Preparation of Compound No. 8

n HO N-N N02 cHscoNH-- O S62CH5 O2 NH t llll-l iilr IO IO I-CONH- (CH2)4-OQ/O -c-anr i To a mixture of 3.2 g. (0.006 mol) of4-acetamido-5-hydroxy-8-(2-methylsulfonyl-4mitrophenylazo)-2- naphthalenesulfonylchloride and 3.9 g. (0.006 mol) of 4-(m-aminobenzenesulfonamido)-N[4-(24-di-t-pen- The method used in Example 1 was used to prepare thiscompound. The yield was 19%, mp. 26870C. dec. The4-acetarnido-5-hydroxy-8-(Z-methylsulfonyl-4-nitrophenylazo)-2-naphthalenesulfonyl chloride was prepared in amanner similar to that used for Exampletylphenoxy)butyl]-l-hydroxy-2-naphthamide in 75 ml. 3. The yield was69%. The 4-acetamido-5-hydroxy-8- of tetrahydrofuran was added 3.0 ml.of pyridine. The (2-methylsulfonyl-4-nitrophenylazo)-2-naphthalenemixture was stirred at room temperature for one hour.sulfonic acid was prepared by a similar method to that under nitrogen,then filtered and the filtrates diluted to used in Example 1 using abasic solution of 4- 500 ml. with hexane. The solid was collected on afilter acetamido-S-hydroxy-Z-naphthalenesulfonic acid in funnel anddried. After chromatography of the solid place of Solution A. The yieldwas 100%. using silica gel and ethyl acetate, the yield of product was1.0 g. (15%) with indistinct m.p.

EXAMPLE 9 Preparation of Compound No. 9 EXAMPLE 7 Preparation ofCompound No. 7

H CQHHHT that used in Example 8 in If]?! yield. mp indistinct.

This compound was prepared in a manner similar to that used in Example 8except that it was chromatographed in the presence ofdiisopropylethylamine. The yield was 17%, mp. l50C.

EXAMPLE 1 1 Preparation of Compound No. 11

This compound was prepared via the method explained in Example 1, in 50%yield, m.p. l957C. dec. The4-aeetamido-8-(2-chloro-4,6-dinitrophenylazo)-5-hydroxy-2-naphthalenesulfonylchloride was prepared in a manner similar to Example 3 in 85% yield. The4-acetamido-S-(2-chloro-4,6-dinitrophenylazo)-S-hydroxy-2-naphthalenesulfonicacid was prepared via the method used in Example 3 in 53% yield.

EXAMPLE l2 Photographic Testing The above image dye-providing compoundswere tested for reactivity and diffusibility of their released dyes to areceiving element. Each compound was dis solved in an equal weight ofdiethyllauramide and finely dispersed in gelatin. The dispersion wasadded to a 0.8 pm monodispersed negative-working gelatino-silver bromideemulsion which was coated on a polyester film support, the coverage ofcompound being about l.1 X moles/dm silver 9.2 mgldm and gelatin 32mgldm An overcoat layer of 8.6 g/dm of gelatin, hardened by formaldehydewas then applied.

A. Image discrimination A sample of the above coating was exposedthrough a step-wedge and then laminated to a mordantcontaining receivingelement with a viscous processing composition (gOO) by passing thesandwich between a pair ofjuxtaposed pressure applying rollers. Thereceiving element consisted of a paper support on which was coated amixture of gelatin (2l mgldm and a mordant,polylstyrene-co-N-benzy1-N,N-dimethyl-N-( 3-maleimidopropy1 )ammoniumchloride] (21 mg/dm"). The goo contained, per liter of solution, 20 g.sodium hydroxide, 0.75 g.4-hydroxymethyl-4-methyl-l-phenyl-3-pyrazolidone, 10 g. potassiumbromide and 25 g. hydroxyethylcellulose. After 60 seconds, the receiverwas peeled apart and washed in water to adjust the pH to about 7. Goodimage density in the exposed areas was obtained with practically notransfer of dye in the unexposed areas. The D max and Dmin for eachtransfer is given under image discrimination in the table.

B. spectrophotometry The spectra of the released dyes when adsorbed tothe mordant on a transparent support were measuredspectrophotometrically. The maximum wavelength (Amax) and the bandwidthin nm at one-half the density of the Amax of the curve for each dye isalso given in the table. This half bandwidth" along with the Amax isindicative of hue, the brightness and purity of color being greater, thesmaller the half bandwidth.

C. Dye-transfer in receiving element Another sample of an emulsioncoating containing the image dyeproviding compound was fogged byexposure to light and processed by passing it as a sandwich with animage receiving element and viscous developing composition (goo) betweena pair of juxtaposed pressure-applying rollers. The developer layerthickness of the resulting laminate ranged from about 0.075 to 0.10 mm.The receiving element had the following structure (the coverages inmg/dm are shown in parenthesis):

Carbon (27) Gelatin l7) TiO (215) +Gelulin (21) Mordant (21) Gelatin ll) Cellulose acetate support Same as above.

The goo" contained 20 g. sodium hydroxide, 0.75 g.4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g. potassiumbromide and 25 g. hydroxyethylcellulose, all per liter of solution. Uponapplication of the goo to the fogged emulsion layer, the dyes arereleased and diffuse through the carbon and titania layers to themordant layer. The density of the dyes on the mordant layer was readthrough the support by means of a reflection densitometer afterintervals of 30, 60 and seconds at 24C. The increase in density, asindicated by the values in the table, is a measure of the rate ofrelease and also of the diffusivity of the dyes.

PHOTOGRAPHIC PROPERTIES Image Discrimination Density of Dye TransferImage Compound Half-band Coverage Coverage of max width (moles X l"(moles X 10 Example (nm) (nml per dm") Dmax Dmin per dm) 30 sec. 60 sec.120 sec.

| 639 119 II 2.70 0.72 11 0.33 0.84 2.04 2 634 113 11 1.80 0.70 11 0.351.04 1.92 3 645 115 ll 2.60 0.44 11 0.64 1.48 2.30 4 645 I33 11 3.201.46 11 0.77 1.29 1.78 5 637 132 11 1.20 0.20 6 0.24 0.35 0.58 h 6L5 I306 1.52 0.50 6 0.36 0.71 1.10 7 622 132 6 2.10 0.71 6 0.32 0.76 1.43 8669 114 6 3.00 0.52 b 0.51 1.11 1.98 9 653 110 6 1.45 0.50 6 0.42 0.891.50 10 640 122 6 2.70 0.68 6 0.81 1.63 2.35 ll 660 I ll 2.84 0.56 60.20 0.46 0.85

EXAMPLE l3 Preparation ofCompounds l2 and 1221 A mixture of 3 g. NaHCO;4.93 g. (8.10 mmol) Compound A, and 3.97 g. (8.10 mmol) of 1-hydroxy-4amino-N-[4-(2,4-di-t-pentylphenoxy)butyll-Z-naphvelopment with asolution of ethyl acetate (9 parts by volume) and methanol (1 part byvolume). A schematic representation of the reactions involved is shownbelow:

thamide (referred to below as NH Group) in g. dry Step dimethylsulfoxidewas stirred at -l00C. for 60 minutes. cooled and poured onto ice watercontaining o H H T I0! t oo 1 1 1 -x O- I I 1 T/ o-o NHZ 5O2F 1 -SO2FStep 2 o H 9 I0: t o o-o IO I CI HSO4N2-0 Q NO2 I If a e? \T/ LH 02cm Hh=N0 O -N0z 02 60-0 12;: I S aCHo O SOzF I-$O F Step 3 A. HzN-Group E-33g I O I 0! sufficient dilute HCl to neutralize the excess NaHCO Theprecipitated Compound 12 was filtered, washed with water. and air dried(crude dye cake yield 102% Compound 12 was quite clean as isolated butwas chromatographed on a silica gel-cellulose (equal parts by weight)dry packed column by ascending dep LsozNH-Group The compound was testedas in Example 12 and the released dye had a )tmax of 640 nm and Dmax of2.35 at 60 seconds and 2.5 at seconds. A similar compound (Compound 12a)having a cyano radical in place of the methylsulfonyl on the nitrophenylring also gave good results.

EXAMPLE l4 Preparation of Compounds l3, l3a, 13b and l3c water wascooled to C. and added dropwise to a 10 solution of 1 ml. 37% HCl in 20ml. of water at 0C. The diazotization was very rapid-the resultingsuspension of diazonium salt was slowly added at 5C. to the couplersolution. The coupling was rapid (probably Compound 13 was tested as inExample l2 and found to have a transferred Amax 660 nm, densities: 0.33(30 sec.), 0.66 (60 sec.) and L08 (l20 see).

A similar compound (Compound l 3a) having a sulfamoyl (-SO NH radical inplace of the sulfo (SO;,H) radical on the nitrophenyl ring was preparedand tested as in Example 12. This compound was found to have atransferred )tmax 640 nm, D max 0.82, densities: 053 (30 seconds), 0.7l((10 seconds), and 0.82 (l seconds).

A similar compound (Compound [311) having a methylsulfonyl (-SO CHradical in place of the sulfo radical on the nitrophenyl ring wasprepared and tested Complete ft minutes at 5 however1 m 15 as in Examplel2. This compound was found to have a ture was Stirred at 2 hours andthe dye PrECiPi, transferred Amax 640, D max 2.03. densities: 0.85 tatedby the addition ofice water. The orange-red pow- (30 Seconds) Seconds) ll 20 cler Compound l3 which was filtered, washed with cold Duds). water(5 liters) and vacuum dried was purified by chro- I A Slmllal' compoulldlcflmpound having matography on a Silica gepcenulose (equal parts by 20isopropylsulfonyl radical in place ofthe sulfo radical on weight) drypacked column by ascending development the mtrophenyl gave good result-5with a solution of chloroform (8 parts by volume) and methanol (2 partsby volume). A schematic representa- EXAMPLE [5 tion of the reactionsinvolved is shown below.

25 An image dye-providing compound of the following structure wasprepared (Compound 14). Step I 0 E i com 4'\ s 1 I g I yams). j E I 0:.10 C o 020; HzN H i L fi-SOzCl O- O .4 pyridinelH NGroup :I M He H2NGroup HzN F/ OH H2 Q O Cl-lsEzla Ha I4o 7 e$ l HN-(CH2J4O' f-ECHzCHa foz. H; T 0

NH SOEH'HGFOUP h 0: '\I I/.

Step 2 H Y s H f\ 0 E m I a \T 4 s --o NH N=N' -NC2 T u I Nz- ---oz o O\O CHaCGzH 4 SOaH Y o 6 CHaCHzCOaH NH 0 10 I Compound 13 O \0/ SO2NHGroup9 is similar to Compound l2 of Example l3 only the hydroxy radical inthe para position (relative to the t 1C T point of attachment of the azolinkage) of the naphtha- (CH2)2 lene nucleus is replaced with OCOCHCompound /O N a 5 I6 is prepared in a similar manner only usingpropionvl 2 H l Q. chloride in the csterificatlon process. C.\ Thesecompounds are tested as in Example l2 with the following results:Compound )tmax ot trans of ferred image 640 nm, densities 1.36 (30 see2.11 (60 10 sec). 2.7 (120 see); Compound l6: )tmax of trans- The abovecompound in diethyllauramide solvent ferred image 640 nm,densities Isee). L95 (60 was coated as a dispersion in gelatin on polyester sup-8C) and Z4 port. Th layer Contained 7.l. l4, and 2! mg/dm of In a likemanner, the hydroxy group in the para posi compound, solvent, andgelatin. respectively. A second tion relative to the point of attachmentof the azo linklayer contained agelatino-silver bromoiodide emulsion 15age of the naphthalene nucleus on Compound 12 is with l l mg/dm ofsilver and 22 mg/dm of gelatin. The replaced with the following groupsand tested as in coating was exposed. dipped in the processing compo-Example l2 with the following results:

AMax Density of Dye Transfer Image Compound Group (nm.) D Max 30 sec. 60sec lZU sec.

9 ,o-o l7 0C0- 0-0 640 13 .77 1.4a 2.3

il 0 -0 i8 435-: O-Cl 640 2.0 .70 1.26 m

Q o-0 19 640 2.9 l.4l 2,4 2.9

ll 20 0C-C.,Hfi 640 1.18 .50 .77 Us 0 o-o 2l -oE- 0 e40 .26 47 .79

sition below for 30 seconds and laminated for varying EXAMELE 17 timeswith a receiving element conta ning a mordant y Such as those releasedfrom the previgusly disk layer of p0ly'4'l'mylpyndme n polyvmpyl alcohola cussed carriers (Car) during alkaline processing P P? PW T Process'ngE m were prepared and dissolved in 30 ml. Ora 0.5N sodium (glmer,solunon water) potasslum t i f' hydroxide solution containing 30 g./l.of hydroxyethyl- (so) potabslum brOmlde (4O)' N'b'enzyl'afplcohmumcellulose. Each solution was spread between a cellulose hromlde (20)berlmtllazole (2O and Sodmm Sulfate acetate cover sheet and a receivingelement so that the (50) Upon delammatlon of Separate "P alkaline dyecomposition was (H mm thick. The reand U0 Sficondsi respectwely'reflectlon denslues ceivirig element was as described in Example l2 onlyof I20, 1.55, and 1.80 were measured on the receiver. having anadditional Myer of gelatin (43 mg/dmz) EXAMPLE 16 Preparation ofCompounds 5-21 coated over the carbon-gelatin layer. The spectra of theCompound l2 of Example 13 is esterified with acetyl chloride in dryacetone using one equivalent of pyridine as the hydrogen chlorideacceptor. Compound l5 dyes when adsorbed to the mordant were determinedin Example l2. The following Table ll shows the general formula of thedyes tested and the results obtained.

dodecylhydroquinone (O mg./ft.*); 7. magenta image dye-providingcompound (150 mg.lft.) having the formula An integral multicolorphotosensitive element is prepared by coating the following layers inthe order recited on a transparent cellulose acetate film support:

I. image-receiving layer of copoly[styrene-N-benzyl- N ,N-dimethyl-N-(3-maleimidopropyl)amrnonium chloride] (200 mg./ft.*) and gelatin (I00mg./ft.*); YH 0-o 2. reflecting layer of titanium dioxide 2000 m mfi)C0NH(CHz)4O0 --c6Hii and gelatin (200 mg./ft. I a 3. opaque layer ofcarbon black (250 mgJft?) and 4 CBHH gelatin (312 mgjfti & 4"' 4. cyanimage dye-providing Compound 12 prepared H502 in Example 13 mg./ft. andgelatin :00 HCH: mg./ft.); H3 5. red-sensitive, internal-imagegelatin-silver chloro- 65 I N=N i bromide emulsion mg. gelatin/ft. and 44 mg. silver/f0), 2,5-di-sec-dodecylhydroquinone I ,I 0 I (25 mgi/ft?)and nucleating agent formyl-4- o methylphenylhydrazine (l g./mole ofsilver); 5H OzNHz

1. A CYAN IMAGE DYE-PROVIDING COMPOUND HAVING A FORMULA AS FOLLOWS:1-((2-D,4-(O2N-),6-E-PHENYL)-N=N-),4-G,((BALL-)(=CH-CH= WHEREIN BALLREPRESENTS AN ORGANIC BALLASTING GROUP CONTAINING AT LEAST 8 CARBONATOMS WHICH RENDERS SAID COMPOUND NONDIFFUSIBLE IN A PHOTOGRAPHICELEMENT DURING DEVELOPMENT IN AN ALKALINE PROCESING COMPOSITION, YREPRESENTS THE CARBON ATOMS NECESSARY TO COMPLETE A BENZENE ORNAPHTHALENE NUCLEUS, X REPRESENTS -R2-LR-R2P- WHERE EACH R2 CAN BE THESAME OR DIFFERENT AND EACH REPREENTS ALKYLENE HAVING 1 TO 8 CARBONATOMS, PHYLENE, OR PHYLENE SUBSTIYUTED WITH CHLORO, BROMO, CYANO,BNITRO, METHOXY, METHYL, CARBOXY OR SULFO, L REPRESENTS OXY, CARBONYL,CARBOXYAMIDO, CARBOMOYL, SULFONAMIDO, SUFAMOYL, SULFONYL OR SULFONYL, NIS AN INTEGER HAVING A VALUE OF - OR 1, P IS 1 WHEN N EQUALS 1 AND P IS1 OR 0 WHEN N EQUALS 0, PREVIDED THAT WHEN P IS 1 THE CARBON CONTENT OFTHE SUM OF BOTH R2 RADICALS DOES NOT EXCEED 14 CARBON ATOMS; RREPRESENTS HYDROGEN OR ALKYL HAVING 1 TO 6 CARBON ATOMS, J REPREENTSSULFONYL OR CARBONYL, M AND Q EACH REPRESENT AN INTEGER HAVING A VALUEOF 0 OR 1, Q REPRESENTS HYDROGEN, HYDROXY OR -NHCOR3 OR -NHSO2R3 WHEREINR3 IS ALKYL HAVING 1 TO 6 CARBON ATOMS, ALKYL HAVING 1 TO 4 CARBON ATOMSSUBSTITUTED WITH HYDROXY, CYANO, SULFAMOYL, CARBOXY OR SULFO, BENZYL,PHENYL, OR PHENYL SUBSTITUTED WITH CARBOXY, CHLORO, METHYL, METHOXY ORSULFAMOYL, G. REPRESENTS HYDROXY, AN ALKALI METAL SALT THEREOF, APHOTOGRAPHICALLY INACTIVE AMINE SALT THEREOF OR A HYDROLYZABLE ACYLOXYGROUP HAVING THE FORMULA: R4-COO- OR R4-O-CO-OWHEREIN R4 IS ALKYL HAVING1 TO 18 CARBON ATOMS, PHENYL OR PHENYL SUBSTITUTED WITH CHLORO OR NITRO;D REPRESENTS CHLORO, BROMO, FLUORO, CYANO, NITRO, TRIFLUOROMETHYL, ALKYLHAVING 1 TO 6 CARBON ATOMS, ALKOY HAVING 1 TO 6 CARBON ATOMS, CARBOXY,-COOR4 WHEREIN R4 IS AS DESCRIBED PREVIOUSLY, FLUOROSULFONYL,-SO3-PHENYL OR SO3-PHENYL SUBSTITUTED WITH HYDROXY, CHLORO, CARBOXY,SULFAMOYL, METHYL OR METHOXY, SULFO, -SO2NR5R6 WHEREIN R5 REPRESENTSHYDROGEN OR ALKYL HAVING 1 TO 6 CARBON ATOMS AND R5 REPRESENTS HYDROGENOR ALKYL HAVING 1 TO 6 TO 6 CARBON ATOMS, ALKYL HAVING 1 TO 4 CARBONATOMS SUBSTITUTED WITH HYDROY, CYANO, SULFAMOYL, CARBOXY OR SULFO,BENZYL, PHENYL, PHENYL SUBSTITUTED WITH HYDROXY, SULFONYL, SULFAMOYL,CARBOXY OR SULFO, ALKYLCARBONYL HAVING 1 TO 6 CARBON ATOMS,ORPHENYLCARBOXYL, WITH THE PROVISO THAT THE CARBON CONTENT OF THE SUM OFR5 AND R6 NOT EXCEED 14 CARBON ATOMS, -CON(R5)2 WHEREIN EACH R5 CAN BETHE SAME OR DIFFERENT AND IS AS DESCRIBED PREVIOUSLY, ALKYLSULFONYLHAVING 1 TO 8 CARBON ATOM, AKYLSULFONYL HAVING 1 TO 6 CARBON ATOMSSUBSTITUTED WITH HYDROXY, PHENYL, CYANO, SULFAMOYL, CARBOXY OR SULFO,PHENYLSULFONYL, PHENYLSULFONYL SUBSTITUTED WITH HYDROXY, SULFONYL,SULFAMOYL, CARBOXY OR SULFO, OR D REPRESENTS((BALL-)(=CH-CH=C(-OH)-Y-)>C-NH-SO2-(X-(N(-R)-J)Q)M- OR PROVIDED THATTHE ((BALL-)(=CH-CH=C(-OH)-Y-)>C-NH-SO2-(X-(N(-R)-J)Q)MON THENAPHTHALENE NUCLEUS OF FORMULA I IS REPLACED BY M OR THE((BALL-)(=CH-CH=C(-OH)-Y-)>C-NH-SO2-X-J-NHC(-OH)-Y-)>C-NH-SO2-(X-(N(-R)-J)Q)M-),Q-NAPHTHALENE OR
 2. A compound as described in claim 1 whereinR2 represents alkylene having 1 to 4 carbon atoms, phenylene orphenylene substituted with carboxy, chloro, methyl or methoxy; Lrepresents sulfamoyl, sulfonamidO, carbamoyl, or carboxamido; Rrepresents hydrogen; q is an integer having a value of 1; m is aninteger having a value of 0 or 1; Q represents hydrogen, hydroxy,-NHCOR3 or -NHSO2R3 wherein R3 represents alkyl having 1 to 4 carbonatoms, alkyl having 1 to 4 carbon atoms substituted with hydroxy, cyano,sulfamoyl, carboxy or sulfo; benzyl, phenyl, phenyl substituted withcarboxy, chloro, methyl, methoxy or sulfamoyl; D represents chloro;fluoro; bromo; cyano; trifluoromethyl; nitro; fluorosulfonyl;alkylsulfonyl having 1 to 6 carbon atoms; alkylsulfonyl having 1 to 6carbon atoms substituted with hydroxy, phenyl, cyano, sulfamoyl,fluorosulfonyl, carboxy or sulfo; phenylsulfonyl; phenylsulfonylsubstituted with hydroxy, sulfamoyl, fluorosulfonyl, carboxy or sulfo;-SO2NHR6 wherein R6 is hydrogen, alkyl having 1 to 4 carbon atoms oralkyl having 1 to 4 carbon atoms substituted with hydroxy, cyano,sulfamoyl, carboxy, or sulfo; benzyl, phenyl or phenyl substituted withhydroxy, sulfonyl, sulfamoyl, carboxy or sulfo; -CON(R5)2 wherein R5 ishydrogen or methyl, and D represents
 3. A compound as described in claim2 wherein n and p each have a value of
 0. 4. A compound as described inclaim 2 wherein m has a value of
 0. 5. A compound as described in claim2 wherein G is a hydroxy radical.
 6. A compound as described in claim 2wherein E represents hydrogen; and M represent hydrogen.
 7. A compoundas described in claim 2 wherein
 8. A compound as described in claim 7wherein X represents
 9. A compound as described in claim 7 wherein -Ballis linked to the sulfonamidonaphthol nucleus, through a
 10. A compoundas described in claim 8 whereiN -Ball represents
 11. A cyan imagedye-providing compound having the formula
 12. A compound as described inclaim 8 wherein -Ball represents
 13. A compound as described in claim 10wherein G represents hydroxy.
 14. A compound as described in claim 12wherein G represents hydroxy.